Ionic fragmentation products of benzonitrile as important intermediates in the growth of polycyclic aromatic hydrocarbons.

In various astronomical environments such as the interstellar medium or (exo)planetary atmospheres, an interplay of bottom-up growth and top-down destruction processes of (polycyclic) aromatic hydrocarbons (PAHs) takes place. To get more insight into the interplay of both processes, we disentangle the fragmentation and formation processes that take place upon dissociative ionization of benzonitrile. We build on previous spectroscopic detections of the ionic fragmentation products of benzonitrile and use these as reactants for low-temperature bottom-up ion-molecule reactions with acetylene. By combining kinetics and infrared action spectroscopy, we reveal exothermic pathways to various (polycyclic) aromatic molecules, including the pentalene and phenylacetylene radical cations. We determine the reaction rate coefficients and unambiguously assign the structures of the reaction products. The data is supplemented by potential energy surface calculations and the analysis of non-covalent interactions. This study shows the unexpected formation of a linked four- and six-membered ring structure (phenylcyclobutadiene radical cation) with molecular formula CH˙, and not the commonly observed isomer naphthalene˙. All observed reactions proceed radiative association processes and are relevant for the chemistry in (cold) astrochemical environments.